Nitrogenous condensation products



PM Au 14, 1945 Heinrich Ulrich, Imlwlsshalen-on-ths-Rhln Germany is,

General assignor, by meme assignmen to Aniline&l 'ilm0orporation,NewYorN. Y.. a corporation of Delaware No Drawing. Application December 12,me, So-

nu No. stats-z. in Germany sum 7, ms

The present application is. a continuationin-part of application Ser.No. 93,787, filed in the name of Heinrich Ulrich on August 1, 1936, nowPatent No. 2,272,489, granted February 10, 1942.

The present invention relates to new nitro enous condensation products.

.I have found that very valuable nitrogenous products are'obtained bycausing 1.2-alkylene imines (ethylene imines) or the non-crystallinehigh molecular products obtainable therefrom by polymerization to reactwith carboxylic acids, their anhydrides or esters. It makes nosubstantial difference in the course of the reaction whether themonomeric imines or their noncrystalline polymerization products areemployed. The latter are preferably obtained by catalytic polymerizationaccording to U. S. Patent 2,182,306. These products have a molecularweight which is more than three times that of the monomeric imines; theyare not so thinly liquid as the monomeric compounds but from viscous towaxy products. Most probably they are mixtures of polymers of differentdegree of polymerization. For example ethylene imine, methylethyleneimine, alpha-beta butylene imine, alpha-beta-dodecylene imine and theirnoncrystalline polymerization products of any desired degree ofpolymerization are suitable for the process.

The 1.2-alkylene imines maybe caused to react for example with fattyacids, such as stearic acid,

oleic acid, the fatty acids present in palm kernel oil and coconutoil,furthermore maleic acid, hy-

droaromatlc or heterocyclic carboxylic acids. Instead of the free acidstheir anhydrides or esters may also be employed. Esters ofchlorocarbonic acid'may be employed with advantage.

The reaction conditions are adapted to the initial materials employed.The reaction usually takes place at temperatures between roomtemperature and 100 0., as for example at from 50 to 80 C., but higheror, in the case of especially reactive initial materials, lowertemperatures may be advantageous. Equimolecular proportions of theiniital materials may be allowed to react with each other or the1.2-alkylene imines may be employed in excess. Depending on the natureand relative proportions of the initial materials, and in some cases onthe reaction conditions, products which are soluble or insoluble inwater can be obtained. The use of solvents or diluents, as for examplewater, alcohol, ether, eyclohexanone, toluene, carbon tetrachloride orchlorbenzene is frequently of advantage. The reaction may be carried outunder increased presployed which react only with difliculty it ispreferable to carry out the condensation ina closed vessel underpressure. It may be advantageous to work in the presence of condensingagents. An addition of natural'or synthetic resins is also frequently ofadvantage during the condensation. It may be of advantage to condensethe alkylene imines simultaneously with two or more of the saidcompounds or first with one of the said compounds, the reaction productbeing condensed with another reactive substance. Products which arestill basic may be employed in the form of salts with mineral or organicacids, as for example with fatty acids. J

The condensation products of 1.2-alkylene imines with the carboxylicacid substances may be subsequently alkylated or peralkylated orsubstituents, as for example carboxylic, sulphonic, sulphuric ester orphosphoric acid groups, may be introduced. The introduction ofsubstituents may also be effected by employing, for the reaction withthe alkylene imines,- compounds which already contain the desiredsubstituents. By condensation for example with chlorocarbonic acidesters, th condensation products may be converted into bodies similar tourethanes. Furthermore two or more of the said methods of treatment maybe combined together or carried I out consecutively.

The products obtainable according to this invention are colorless orslightly colored viscous liquid, or wax-like, or solid substances manyof which are dimcultly soluble or insoluble in water but soluble inorganic solvents, the nature of the products obtained depending on theinitial materials and working conditions employed.

The products are suitable for a great variety of purposes; for examplethey may serve alone or together with other suitable substances asassistants for the pharmaceutical, cosmetic, textile, leather, lacquer,rubber and like industries. For example they may be added with advantageto the spinning baths in the preparation of artiiiclal silk; theyincrease the aflinity of artificial silk toacid dyestuffs. The productsmay also be preferable to employ the products in a dissolved ordispersed iorm, for example while employing dispersing agents, as forexample salts oi the sulphuric esters of fatty alcohols or truesulphonic acids of aliphatic compounds oi high molecular weight;

The iollowing examples will further illustrate the nature of thisinvention but theinvention is not restricted to these examples. Theparts are by weight. Example 1 43 parts oi water-soluble polymerizedethylene imine and 25 parts of the mixture oi the chlorocarbonic acidesters of the alcohols corresponding to the iatty acids contained inpalm kernel oil are heated at irom about 50 to 60 C for three hourswhile stirring. As soon as a sample withdrawn Dichloroacetic acid,bromoacetic acid, 'bromostearic acid and the like my be employed insteadof chloroacetic acid.

By treatment with alkyl halide alkyl groups may be introduced into th'emolecule oi the compounds thus obtainable.

Emample 116 parts of maleic acid are condensed with polymeric ethyleneimine. A valuable artificial mass, is iormed by the reaction which isaccompanied by the evolution oi heat.

from the reaction mixture is soluble in water to I give a clearsolution, the reaction is interrupted.

Aqueous solutions of the reaction product thus obtained have anexcellent washing action even in acid and neutral media.

Example 2 225 parts oi. stearic acid anhydride are condensed with 86parts of water-soluble polymerized ethylene imine. The reaction productsare readily colloidally dispersible in water and may be employed asemulsifying agents.

Instead of stearic acid anhydride cetyl chlorocarbonic estermaybeused.

Water-insoluble polymerized ethylene imine may also be used instead ofthe water-soluble product. 7

Example 3 622 parts oi the product obtainable according to the firstparagraph of the preceding example is brought into reaction with 94parts oi chloracetic acid or 118 parts of succinic acid or 72 parts ofacrylic acid. The products thus obtained are soluble in dilute acids andalkali hydroxide solutions.

Example 4 440 parts of solid or liquid polymerized ethylene imine arereacted with 200 parts oi chloroacetic acid. The compound obtained maybe employed for example for the absorption oi acid gases.

Erample c The product obtained according to Example 1 or a urethane-likeproduct prepared thereirom is heated with the equivalent amount or amultiple 01' the equivalent amount of chloracetic acid or chloraceticacid ester. The resulting products may be used for various kinds oitextile improvement.

Emmple 7 consisting oi monomeric 1.2-alkylene'imines and theirnon-crystalline high molecular polymerization products with cetylchlorocarbonicester.

3. Nitrogenous condensation products obtained by condensing a memberselected from the class consisting of monomeric 1.2-a1kylene imine andtheir non-crystalline high molecular polymerize..- tion products with amixture oi the chlorooarbonic acid esters of the alcohols correspondingto a mixture of naturally occurring higher iatty acids.

CH ULRICH.

